Process for breaking petroleum emulsions employing amine-modified thermoplastic phenol-aldehyde resins



PROCESS FOR BREAKING PETROLEUM EMUL- SHONS EMPLOYING AMINE-MODIFIED THER- IVIOPLASTIC PHENOL-ALDEHYDE RESINS Melvin De Groote, University City, Mo., assignor to Petrolite Corporation, Wilmington, Del., a corporation of Delaware No Drawing. Application October 2, 1953,. Serial No. 383,928

Claims. (Cl. 252-344) Attention is directed to my co-pending applications, Serial Numbers 288,742, through 288,746, inclusive, filed l/iay 19, 1952, now abandoned. The first of said co-pendapplications is directed to a process for breaking petroleum emulsions employing a demulsifier including products obtained by condensing certain phenol-aldehyde resins, therein described in detail, with certain basic nonhydroxylated secondary monoamines, also therein described in detail, and formaldehyde.

The second application is similar to the first except that the monoamines employed as reactants are hydroxylated instead of being nonhydroxylated. The third application is similar to the first one insofar that nonhydroxylated polyamines are employed as reactants. The fourth application is concerned with hydroxylated polyamines as reactants and the last application is concerned with amines having a cyclic amidine group in the reactant regardless of whether it is hydroxylated or not.

The present application is differentiated from the aforementioned five applications in that the aldehyde used, instead of being formaldehyde, is glyoxal. Stated another way, this invention is concerned with a proces for breaking petroleum emulsions of the water-in-oil type employing a demulsifier including certain heat-stable oxyalkylaflan-susceptible resinous condensation products obtained by condensing certain phenol-aldehyde resins, hereinafter. described in detail, with certain basic secondary amines, also hereinafter described in detail, and glyoxal.

For purpose of illustration it may be simpler to divert momentarily to the products described in the five aforementioned co-pending applications, Serial Nos. 288,742 through and including 288,746, inclusive, and for sake-of simplicity to the first one, i. e., Serial No. 288,742, in which the amine reactant is a nonhydroxylated monoamine. For purpose of simplicity the invention described.

in said co-pending application, Serial No. 288,742, may be exemplified by an idealized formula, as follows:

in which R represents a hydrocarbon substituent generally having 4 and not over 18 carbon atoms but most preferably not over 14 carbon atoms, and n generally is a small whole number varying from 1 to 4. In the resin structure it is shown as being derived from formaldehyde although obviously other aldehydes are equally satisfactory. The amine residue in the above structure is derived from a basic amine, and usualy a strongly basic amine, and may be indicated thus:

R in which R represents anyappropriate hydrocarbon radical, such as an alkyl, alicyclic, arylalkyl radical, etc., free from hydroxyl radicals. The only limitation is that the radical should not be a negative radical, which considerably reduces the basicity of the amine, such as an aryl radical or an acyl radical. Needless to say, the two occur rences of R may jointly represent a single divalent radical instead of two monoyalent radicals. This is illus trated by morpholine and piperidine': The introduction of two such amino radicals into a comparatively small resin molecule, for instance, one having 3 to 6 phenolic nuclei as specified, alters the resultant product in a rium' ber of ways. In the first place, a basic nitrogen atom, of course, adds a hydrophile effect; in the second place, depending on the size of the radical R, there may be a counterbalancing hydrophobe effect or one in which the hydrophobe effect more than counterbalances the hydrophile effect of the nitrogen atom. Finally, in such cases where R contains one or more oxygen atoms, another effect is introduced, particularly another hydrophile effect.

Such condensates, i. e., the condensates of Serial No. 288,742, and in fact the instant condensates, are obtained from phenol-aldehyde resins. It is well known that one can readily purchase on the open market, or prepare fusible, organic solvent-soluble, water-insoluble resin polymers of a composition approximated in an idealized form by the formula R R n R In the above formula n represents a small whole number varying from 1 to 6, 7 or 8, or more, up to probably 10 or 12 units, particularly when the resin is subjected to heating under a vacuum as described in the literature. A limited sub-genus is in the instance of low molecular weight polymers where the total number of phenol nuclei varies from 3 to 6, i. e., n varies from 1 to 4; R represents a hydrocarbon substituent, generally an alkyl radical having from 4 to 14 carbon atoms, such as a butyl, amul, hexyl, decyl or dodecyl radical. Where the divalent bridge radical is shown as being derived fromformaldehyde it may, of course, be derived from any other reactive aldehyde having 8 carbon atoms or less. When a phenol-aldehyde resin amine condensate is prepared using glyoxal instead of formaldehyde, particu larly if molecular equivalents are employed, that is, one mole of glyoxal to replace 2 moles of formaldehyde, it becomes apparent that certain other modifications can and do take place with the resultthat one obtains a molecule having a different structure and in many instances a comparatively higher molecular Weight. All that is necessary is to reconsider the condensate in terms of the over-simplified structure previously. noted, to wit:

For convenience, this formula can be abbreviated somewhat, thus:

If glyoxal is used it is apparent an entirely different Patented May 14, 1957 structure is obtainable. This structure, at least an inner segment thereof, can be shown thus:

Reverting again to what is said in the five copending applications previously referred to, and particularly to Serial No. 288,742, reference is made to the text which describes other products of reaction which appear in the cogeneric mixture resulting from reaction between the resin, the secondary amine and formaldehyde. The reference is as follows:

In conducting reactions of this kind one does not necessarily obtain a hundred percent yield for obvious reasons. Certain side reactions may take place. For instance, 2 moles of amine may combine with one mole of the aldehyde, or only one mole or the amine may combine with the resin molecule, or even to a very slight extent, if at all, 2 resin units may combine without any amine in the reaction product, as indicated in the following formulas:

When formaldehyde is replaced by glyoxal, in light of what has been said it becomes apparent that the three above formulas could be written showing dimeric or trimeric forms of each structure rather than the monomer. ver and above this combinations could take place between any one of the three above or any one of the three with the condensate previously depicted.

In any event, to the extent that in a reaction mass formaldehyde is replaced by glyoxal it becomes apparent that amore complicated and an entirely different structure, or structures, are obtainable. In many instances where formaldehyde gives a condensate which is a highly viscous liquid the use of glyoxal results in a solid. Furthermore', the molecular Weight to the extent that its determination can be made or approximations can be made, seem to be distinctly higher in molecular weight. In any event, the condensates so obtained are different in character and for some purposes particularly after oxyalkylation with ethylene oxide, propylene oxide, butylene oxide, glycide, or methylglycide are particularly effective for the resolution of petroleum emulsions. Indeed, in many instances the oxyalkylation derivatives are distinctly more effective than the comparable products derived from condensates in which formaldehyde is used.

For purpose of convenience what is said hereinafter will be divided into four parts:

Part 1 is concerned with phenol-aldehyde resins suitable for condensation;

' phenolformaldehyde resin.

PART 1 This part is concerned with the preparation of phenolaldehyde resins of the kind described in detail in U. S. Patent No. 2,499,370, dated March 7, 1950, to De Groote and Keiser, with the following qualifications; said aforementioned patent is limited to resins obtained from difunctional phenols having 4 to 12 carbon atoms in the substituent hydrocarbon radical. For the present purpose the substituent may have as many as 18 carbon atoms, as in the case of resins prepared from tetradecylphenol, substantially para-tetradecylphenol, commercially available. Similarly, resins can be prepared from hexadecylphenol or octadecylphenol. subsequently.

In additionto U. S. Patent No. 2,499,370, reference is made also to the following U. S. patents: Nos. 2,499,365, 2,499,366, and 2,499,367, all dated March 7, 1950, to De Groote and Keiser. These patents, along with the other two previously mentioned patents, describe phenolic resins of the kind herein employed as initial materials.

For practical purposes, the resins having 4 to 12 carbon atoms are most satisfactory, with the additional C14 carhon atoms also being very satisfactory. The increased cost of the C16 and C18 carbon atom phenol renders these raw materials of less importance, at least at the present time.

Patent 2,499,370 describes in detail methods of preparing resins useful as intermediates for preparing the products of the present application, and reference is made to that patent for such detailed description and to Examples 1a through 103a of that patent for examples of suitable resins.

As previously noted, the hydrocarbon substituent in the phenol may have as many as 18 carbon atoms, as illustrated by tetradecylphenol, hexadecylphenol and octadecylphenol, reference in each instance being to the difunctional phenol, such as the orthoor para-substituted phenol or a mixture of the same. Such resins are de scribed also in issued patents, for instance, U. S. Patent No. 2,499,365, dated March 7, 1950, to De Groote and Keiser, such as Example 71a.

Reference has been made to an earlier formula which was in essence an over-simplification representing a Actually, some other aldehyde, such as acetaldehyde, propionaldehyde, or butyraldehyde, may be used. The resin unit can be exemplified thus:

OH I" OH OH I nr Ir/ in which R is the divalent radical obtained from the particular aldehyde employed to form the resin.

As previously stated, the preparation of resins of the kind herein employed as reactants is well known. See U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote and Keiser. Resins can be made using an acid catalyst or basic catalyst or a catalyst showing neither acid nor basic properties in the ordinary sense, or without any catalyst at all. It is preferable that the resins employed be substantially neutral. In other Words, if prepared by using a strong acid as a catalyst, such strong acid should be neutralized.v Similarly, if a strong base is used as a catalyst, such strong acid should be neutralized.

This feature will be referred to Similarly, if a strong base is used as a catalyst it is preferable that the base be neutralized although we have found that sometimes the reaction described proceeded more rapidly in the presence of a small amount of free base. The amount may be as small as a 200th of a percent and as much as a few tenths of a percent. Sometimes moderate increase in caustic soda and caustic potash may be used. However, the most desirable procedure in practically every case is to have the resin neutral.

In preparing resins one does not get a single polymer, i. e., one having just 3 units, or just 4 units, or just 5 units, or just 6 units, etc. It is usually a mixture; for instance, one approximating 4 phenolic nuclei will have some trirner and pentamer present. Thus, the molecular weight may be such that it corresponds to a fractional value for n as, for example, 3.5, 4.5 or 5.2.

In the actual manufacture of the resins we found no reason for using other than those which are lowest in price and most readily avail-able commercially. For purpose of convenience suitable resins are characterized in the following table:

TABLE 1 M01. wt. Ex- Position R? of resin ample R of R derived n molecule number from (based on n+2) 1a Phcnyl Para. 3. 5 992. 5

Tertiary butyl do 3.5 882. 5 Secondary butyl.-- Ortho 3. 5 882.5 Cyclo-hexyl Para. 3. 5 1, 025. 5 Tertiary amyl do 3. 5 959. 5 Mixed secondary Ortho... 3. 5 805. 5

and tertiary amyl.

Para 3. 5 805. 5 3. 5 1, 036. 5 3. 5 1, 190. 5 3. 5 1, 267. 5 3. 5 l, 344. 5 Dodecyl 3. 5 1, 498. 5 Tertiary butyl 3. 5 945. 5

Tertiary amyl d 3. 1,022. 5 Non do. 3. 5 1, 330. 5 Tertiary butyl. r do 3. 5 1, 071. 5

do 3. 5 1, 148. 5 Y y -do 3. 5 1, 456. 5 Tertiary butyl .do 3. 5 1,008. 5

20a Tertiary amyl do 3. 5 1, 085.5 2141 Nonyl do. 3. 5 1, 393. 5 22a Tertiary butyl .do 4. 2 996, 6

Tertiary amyl .do 4. 2 1, 083. 4 N011 do 4.2 1, 430.6 Tertiary butyl do 4. 8 1, 094. 4 Tertiary amyl H do 4. 8 1, 189. 6 Nonyl do 4. 8 1, 570. 4 Tertiary amyl. do, 1. 5 604. 0 1. 5 (S46. 0 1. 5 653. 0 1. 5 688.0

2.0 692.0 yl 2.0 748. 0 Cycle-hexyl o.. do 2.0 740. 0

PART 2 As noted previously, a variety of secondary amines free from a primary amino group may be employed. These amines fall into five categories, as indicated previously.

One category consists of strongly basic secondary monoamines free from hydroxyl groups whose composition may be indicated thus:

\NE{ a in which R represents a-monovalent alkyi, alicyclic,

6 arylalkyl radical and may be heterocyclic in a few instances as in the case of piperidin'e and a secondary amine derived from furfurylamine by methylation or ethylation, or a similar procedure.

Another example of a heterocyclic amine is, of course, monpholine.

The secondary amines most readily available are, of course, amines such as dimethylami-ne, methylethylamine, diethylarnine, dipropylamine, ethylpropylamine, dibutylamine, diamylamine, dihexylamine, dioctylamine, and dinonylamine. Other amines include bis(1,3-dimethylbutyl)amine. There are, of course, a variety of primary amines which can be reacted with an alkylating agent such as dimethyl sulfate, diethyl sulfate, an alkyl bromide, an ester of sulfonic acid, etc., to produce suitable amines within the herein specified limitations. For example, one can .i-ethylate alphamethylbenzylamine, or benzylamine itself, to produce a suitable reactant. Needless to say, one can use secondary amines such as dicyclohexylamine, dibutylamine or amines containing one cyclohexyl group and one alkyl group, or one benzyl group and one alkyl group, such as ethylcyclohexylamine, ethylbenzylamine, etc.

Other suitable compounds are exemplified by Other somewhat similar secondary amines are those of the composition as described in U. S. Patent No. 2,375,659, dated May 8, 1945, to Jones et al. In the above formula R may be methyl, ethyl, propyl, amyl, octyl, etc.

Other amines can be obtained from products which are sold in the open market, such as may be obtained by alkylation of cyolohexylmethylamiue or the a lkylation of similar primary amines, or, for that matter, amines of the kind described in U. S. Patent No. 2,482,546, dated September 20, 1949, to Kaszuba, provided there is no negative group or halogen attached to the phenolic nucleus. Examples include the following: beta-phenoxyethylamine, gamma phenoxypropy-lamine, beta phenoxy-alpha-methylethylamine, and betaphenoxy- 2 propylamine.

The secondary category represents secondary amines which are hydroxylated monoamines. These may be illustrated by diethanolamine, methylethanolamine, dipropanolamine, dibutanolamine and ethylpropanolamine. Suitable primary amines which can be so converted into secondary amines include butylamine, amylamine, hexylamine, higher molecular weight amines derived from fatty acids, cyclohexylamine, benzylamine, furfurylamine, etc.

Other suitable amines include 2-amino-1-butanol, 2- amino-Z-methyl-l-propanol, Z-amino 2 methyl,1,3-pro-- panediol, 2-amino-2-ethyl-1,3-propanediol, and hishydroxylmethyl -aminoethane. such amines is illustrated by 4-amino-4-methyl-2-pentanol.

Another example of Other suitable compounds are the following:

(CaHsO 011140 03114) E o 02H4 H O C 114 (OiHnOOH CHmm)(oH )CH0H2) HO C2114 (CHaOCHz0H2OCH2CHzOCH2CH HOCzH (CHaQCHzCHgCHgCHgCHzCHz) 7 HO C2114 or comparable compounds having two hydroxylated groups of dilferent lengths as in (HOCHzOHgOCHgCH OOHzCHfl Other examples of suitable amines include alphamethylbenzylamine and monoethanolamine; also amines obtained by treating cyclohexylmethylarnine with one mole of an oxyalkylating agent as previously described; beta-ethylhexylbutanolamine, diglycerylamine, etc. Another type of amine which is of particularrinterest because it includes a very definite hydrophile group includes sugar amines such as glucamine, galactamine and fructamine, such as N-hydroxyethylglucamine, N-hydroxyethylgalactamine, and N-hydroxyethylfructamine.

Other suitable amines may be illustrated by CH3 HO.OH2.+.CH2OH NH HO.OH2.(:J.CHzOH GHa r 01131 0112011 1TH CHaXILCHzOH See, also, corresponding hydroxylated amines which can be obtained from rosin or similar raw materials and described in U. S. Patent No. 2,510,063, dated June 6, 1950, to Bried. Still other examples are illustrated by treatment of certain secondary amines, such as the following, with a mole of an oxyalkylating agent as described; phenoxyethylamine, phenoxypropylamine, phenoxyalphamethylethylamine, and phenoxypropylamine.

Poly'amines free from a hydroxyl group may be illustrated by the following:

- C,H v 0, 13 NozHaNczHiN N propyleneNpropyleneN CHa The fourth category consists of polyamines haying hydroxylated groups which may be characterized by the following:

CH3 /CH3 NcgfhgczHiN HO CgH4 CzHtOH czHioH CH5 CH3 HOCaHi CgH OH CH3 CH Suitable cyclic amidines which may or may not have a hydroxyl group but are free from primary amino groups may be illustrated by the following: Z-undecylimidazoline Z-heptadecylimidazoline 2-oleylimidazoline 1-N-decylaminoethyLZ-ethylimidazoline Z-methyl,1-hexadecylaminoethylaminoethylimidazoline 1-dodecylaminopropylimidazoline l-(stearoyloxyethyl) aminoethylimidazoline 1-stearamidoethylaminoethylirnidazoline 1-(N-dodecyl)-acetamidoethylaminoethylimidazoline 2-heptadecyl,4,S-dimethylimidazoline l-dodecylaminohexylimidazoiine 1-stearoyloxyethylaminohexylimidazoline 2-heptadecyl,l-methylaminoethyl tetrahydropyrimidine 4-methyl,2-dodecyl,l-methylaminoethylaminoethyl tetrahydropyrimidine of Z-heptadecyl,1-aminoethylimidazoline, which can be illustrated by the following formula:

N-C H2 15 25-0 N-C Hg CzHrOH C2H4.N

Other reactants may be employed in connection with an initial reactant of the kind described above, to wit, 2-heptadecyl,l-aminoethylimidazoline; for instance, reaction with an alkylene imine such as ethylene imine, propylene imine, etc. If reacted with ethylene imine the net result is to convert a primary amino radical into a .seconddary amino radical and also introduces anew primary amine group. If ethylene imine is employed, the net result is simply to convert 2-heptadecyl,1-aminoethylimidazoline into Z-heptadecyl,l-diethylenediaminoimidazoline. However, if propylene imine is vused the net result is a compound which can be considered as being derived hypothetically from a mixed polyalkylene amine,

i. e., one having both ethylene groups and a propylene group between nitrogen atoms.

PART 3 The products obtained by the herein described processes represent cogeneric mixtures which are the result ofa condensation reaction or reactions. Since the resin molecule cannot be defined satisfactorily by formula, although it may be so illustrated in an idealized simplification, it is difiicult to actually depict the final product of the cogeneric mixture except in terms of the process itself.

The herein described amine-modified resins are obtained from glyoxal and not formaldehyde. Generally speaking, the objective in the preparation of these aminemodified resins is to obtain a heat-convertible compound even by using formaldehyde. It is not necessary to point out the complications involved when glyoxal is used. See, for example, U. S. Patent No. 2,031,557 to Bruson. Since the condensation products obtained are not heatconvertible and since temperature up to 150 C. or

thereabouts may be employed, it is obvious that the '10 procedure becomes comparatively simple. Indeed, perhaps no description is necessary over and above what has been said previously, in light of subsequent examples. However, for purpose of clarity the following details are included.

A convenient piece of equipment for preparation of these cogeneric mixtures is a resin pot of the kind described in aforementioned U. S. Patent No. 2,499,368. In most instances the resin selected is not apt to be a fusible liquid at the early or low temperature stage of reaction employed as subsequently described; in fact, usually it is apt to be a solid at distinctly higher temperatures, for instance, ordinary room temperature. T hus, we have found it convenient to use a solvent and particularly one which can be removed readily at a comparatively moderate temperature, for instance, at C. A suitable solvent is usually benzene, xylene, or a comparable petroleum hydrocarbon or a mixture of such or similar solvents. Indeed, resins which are not soluble except in oxygenated solvents or mixtures containing such solvents are not here included as raw materials. The reaction can be conducted in such a way that the initialreaction, and perhaps the bulk of the reaction, takes place in a polyphase system. -However,.if desirable, one can use an oxygenated solvent such as a low-boiling alcohol, including ethyl alcohol, methyl alcohol, etc. Higher alcohols can be used or one can use a comparatively nonvolatile solvent such as dioxane or the diethylether of ethyleneglycol. One can also use a mixture of benzene or xylene and such oxygenated solvents. Note that the use of such oxygenated solvent is not required in the sense that it is not necessary to use an intial resin which is soluble only in an oxygenated solvent as noted, and it isnot necessary tohave a single phase system for reaction.

Glyox al is available as a 30% aqueous solution. In this way it is comparable to formaldehyde which is available as a 37% aqueous solution, and is sometimes used in more dilute form. I have found no difficulty in promoting the condensation reaction although at times it is desirable to add some solvent having a common solvent effect. Thus an oxygenated solvent may or may not be employed. Such solvent may be employed in combination with a hydrocarbon solvent such as xylene. However, if the reaction mass is going to be subjected to some further reaction where the solvent may be objectionable as in the case of ethyl or hexyl alcohol, and if there is to be subsequent oxyalkylation, then, obviously,

the alcohols should not be used or else it should be removed. The fact that an oxygenated solvent need not be employed, of course, is an advantage for reasons stated.

Another factor, as far as the selection of solvent goes, is whether or notthe cogeneric mixture obtained at the .end of the reaction is to be used as such or in the salt form. The cogeneric mixtures obtained are apt to be solidsor thick viscous liquids in which there is some change from the initial resin itself, particularly if some of the initial solvent is apt to remain without complete removal. Even if one starts with a resin which is almost water white in color, the condensation products obtained are invariably dark and particularly reddish or dark red in color.

By and large, the melting point of the condensate is apt to be higher than of comparable condensates obtained by the use of formaldehyde or furfural. As has been suggested previously, this apparently is due to the difunctional property of glyoxal. Indeed, depending on the resin selected andth e amine selected the condensate the amine have entered into reaction.

The products obtained, depending on the reactants selected, may bewater-insoluble, or water-dispersible, or water-soluble, .or close to being water-soluble. Water 11 solubility is enhanced, of course, by making a solution in the acidified vehicle such as a dilute solution, for instance, a solution of hydrochloric acid, acetic acid, hydroxy-acetic acid, etc. One also may convert the ter of convenience. Indeed, using furfural I have usually done nothing more than prepare the reaction mixture, add a suitable amount of xylene, and reflux for approximately 3 to 6 /2 hours at temperatures varying, as the finished product into salts by simply adding a stoichio- 5 Cas may be, from 135 to 160 C. Where the amine has metric amount of any selected acid nd removing any a comparatively low basicity I have sometimes added a Water present by refluxing with benzene or the like. In Small amount or approxlma ely 0f SOd1l1m methylatefact, the selection of the solvent employed may depend P g 2 While-benzene mlXture, Instance, in part whether or not the product at the completion of apprOXlmatelY 170 Parts f benzene 35 Parts Of the reaction is to be converted into a salt form. xylene. and a phaseparating trap to eliminate water, I In the next succeeding paragraph it is pointed out that 318V? fmlild mat I Could. mp y temperatures between frequently it is convenient to eliminate all solvent, using 9 and andfillmlllaie the Water 0f COIIdBDSBe a temperature of not over 150 C. and employing vacuum tlon by reflux ng at this temperature. However, I have if required. This applies, of course, only to those cirfound I10 Partlcular advantag? 115mg thls low mp I cumstances where it is desirable or necessary to remove ur r nd above h g temperature Prevlously the solvent. Petroleum solvents, aromatic solvents, etc., can be used. The selection of solvent, such as benzene, Example xylene, or the like, depends primarily on cost, i. e., the 1 use of the most economical solvent and also on three The Tesm employed was the prevlously desfgnated other factors, .two of which have been mentioned preas 2311 and had a molecular Weight of approximately viously; (a) is the solvent to remain in the reaction mass Q- 175 g ms 0t thl resin were dlssolved in an equal without removal? (b) is the reaction mass to be subjected Welght 0f Xylene d 61 grams of dblsopropallolalflme to further reaction in which the solvent, for instance, an added 53 grams of Y (30% aqueous 801139011) alcohol, either low boiling or high boiling, might i i were added and the mixture stirred for about 30 minutes 0 o o fore as in the case of oxyalkylation? and the th1rd factor and e the temperature allcwed to me to i i hi i an effort to b d t if th reactign where it wasallowed to reflux for 6 hours. During this mass by the usual procedure as, for example, a WaterffifluXlng Period a p ep s p Was 11$ed f wash to remove any unreacted low molal soluble amine, mQVe the Water 0f formatlonv At the and 0f thls 'f if employed and present after reaction? Such procedures the reaction was complete and the product was obtained are well known and, needless to say, certain solvents are in the form of an xylene solution. A small sample was more suitable than others. Everything else being equal, evaporated to eliminate the xylene. The resultant prod- We have found xylene the most satisfactory solvent. not was a highly viscous, tacky material, being black in I have found no advantage in using a low temperature, Color ith a reddi h tinge, approximately room temperature, at the start of the re- Similar products were prepared as indicated in the action although this is sometimes done purely as a matfollowlng table.

TABLE II Solvent (Xylene Max. Resin Glyoxal unless Time temp. Ex. amt., Secondary amine Amt, (30% aq otherwise period, during No. grams grams s0l.), noted), hrs. reaction,

' grams grams C.

175 Di-isopropylaminc G1 58 170 7 145 150 Di-n-butylaminc 48 160 6 160 150 Di-ethylamino 37 48 155 5 143 150 Di-cyc10hexylamiue. 91 48 155 7 170 300 Morpholine s7 95 305 s 145 300 Di-Z-ethylhexylamine 241 96 290 4.5 163 225 Bis-(1,3-dimethylbutyl)amine. 139 72 235 225 Di-isopropanolamina'. 100 72 230 3 160 225 a-Methylbenzylethanolamine- 124 72 235 3 157 225 Di-ethanolamine 79 72 220 2.5 158 225 Aminoethyl ethanolamine 78 72 2 225 Diethanolamine 79 72 55-170 3 100 225 do 79 72 "55470 3 98 225 do 131.5 128 55-170 s so 225 Diisopropanolamine. 174 128 235 1.75 130 r 236 Di-isopropanolamine 61 58 231 7 r 197 Di-n-butylamine 65 48 192 6 197 Diethylamine 37 48 203 5 145 197 Di-cyclohexylamine 91 48 185 7 393 Morpholine 87 96 384 6.5 155 393 Di(2-ethylhexyl)amine 241 96 398 5.0 t 197 N-methylaniline 54 48 102 4 170 295 Di-(bcta-phenylethyl)amine. 169 72 300 4.5 160 295 Di-is0propanolamine 100 72 200 3 155 225 Di-cthanolamine... 79 72 305 2.75 158 188 Di-isopr0pylamine 61 58 220 8 145 188 Di-n-bntylamine 65 48 178 5 162 188 Di-cthylamine.-. 37 48 c 1 145 374 Di-cyclohcxylamin'e 91 48 196 7 163 374 Morpholine 87 96 370 6.5 155 188 Di-(2-ethylhexyl)aruine 241 96 378 4.5 168 280 N-methylu-niline 54 48 198 5 170 280 Di-(bcta-phenylethyhcm 169 72 290 4.5 158 280 Di-isopropanolamine 100 72 270 3 155 280 Di-ethanolamine 79 72 270 2.75 158 Norm-In the above examples no catalyst was added. In some duplications of the above small'amounts of catalyst were added up to 1% to 2% of either powdered caustic soda or powdered sodium mcthylatc. No advantage was noted in the use of a catalyst provided the amine was sufiiciently basic.

In Examples 12b, 13b and 14!) indicated by the double asterisk the solvent was a mixture of 170 parts of benzene and 55 parts of xylene.

The racial ratio of resin to amine toaldehyde was 1 to 2 to 1, except in Examples 14b and 15b where the ratio was 1 to 3.5 to 1.75 in both instances.

I In Examples 1b through 15b the resin employed was the one identified as Example 282. In Examples 16b through 25b the resin employed was the one identified as Example 322, and in Examples 26!) through 3511 the resin employed was identified as Example 39a.

2,792,'s en 13 Returning now to a consideration of the structure of the condensate it becomes obvious that one could obtain ring compounds. Using the abbreviated formula previously applied, the simplest ring could be shown thus:

Obviously, one could have rings with a larger number of members in the ring to say nothing of complications involving alkanol radicals, for instance, the elimination of a hydrogen atom from the alkanol hydroxyl group. Furthermore, the situation becomes even more complicated if the ratios are changed to correspond to ratios described in my co-pending application, Serial No. 376,- 240, filed August 24, 1953. In this particular instance there are described a number of complicated condensates in which 3 /2 moles of diethanolamine, or the like, 3 /2 moles of formaldehyde, and one mole of the phenolaldehyde resin, are employed. If corresponding condensates are prepared, replacing 3 /2 moles of formaldehyde by 1% moles of glyoxal, a variety of compounds are obtained which have unusual structure but are still organic solvent-soluble and susceptible to oxyalkylation.

Indeed, another variety of somewhat more complicated materials are obtained by using as the amine reactant di(hydroxyethyl)N,N'-ethylene diamine having the following structure:

/N NC2H N H CHE-50H HO CaHi An initial product can be made treating the amine as if it were nothing more than a hydroxylated monoamine. Subsequently glyoxal may be added up to, for example, the amount originally employed with the production of linear polymers and in some instances cross-linking. It is understood that regardless of what amine is used the final product obviously is, and must be, organic solventsoluble. The primary objective is to obtain a condensate which is organic solvent-soluble and not an infusible resin. Such condensate is particularly valuable for oxyalkylation. The products so obtained find utility in various arts.

PART 4 As to the'use of conventional "demulsifying agents reference is made to U. S. Patent No. 2,626,929, dated January 7, 1953,'to De Groote, and particularly to Part 3. Everything that appears therein applies with equal force and efiect to the instant process, noting only that where reference is made to Example 13b in said text beginning in column 15 and ending in column 18, reference should 'be to Example 8b, hereindescribed.

Having thus described my invention, what I claim as new and desire to secure by Letters Patent is:

-l. The process ofbreaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including synthetic hydrophile products obtained by condensing (a) an oxyalkylatiomsusceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenolaldehyde resin having an average molecular Weight corresponding to at lea-st 3 and not over 6 phenolic nuclei per resin molecule; said resin being derived by reaction between a difunctional monohy-dric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial- 1 4 absence of phenols of functionality greater than 2; said phenol being of the formula in which 'R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 posit-ion; (12) a basic secondary amine free from any primary amine radical and having not more than 32 carbon atoms in any group attached to any amino nitrogen radical and reactive towards glyox-al; and *(c) glyoxal; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolyt-ic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible.

2. The process of claim 1 with the proviso that .there be an alkanol radical attached to at lea-st one amino nitrogen atom.

3. The process of breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including synthetic hydrophile products obtained by condensing (a) an oxyalkylanon-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenolaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of phenols of functionality greater than 2; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at lion-susceptible.

4. The process of. breaking petroleum emulsions of the Water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including synthetic hydrophile products obtained by condensing (a) an 'oxyalkylation-susceptible, fusible, nonoxygenated organic solvent-soluble, water-insoluble, low-stage phenolaldehyde resin having an average molecular weight corresponding to at. least 3 and not over 6 phenolic nuclei per resinmolecule; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of phenols of functionality greater than 2; said phenol being of the formula c J in iwhi-chlR is anuallpha tichydrocarbon radicalvhaving iati le'ast 4r'andf not more thanf'24carbon atoms and sub- 'stituted in the 2,4,6 position; (b) a basic hydroxylated secondary monoamine having not more than. 32 carbon atoms in any group attached to the amino nitrogen atom and reactive towards glyoxal; and (c) glyoxal; said condensation reaction being conducted at 'a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; with the added proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule; and with the further proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible.

5. The process of breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emul- "sion to the action of a demulsifier including synthetic hydrophile products obtained by condensing (a) an oxyalkylanon-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenolaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of phenols of functionality greater than 2; said phenol being of the formula in, which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom and reactive towards glyoxal; and 2(0) glyoxal; said condensation reaction being conducted at a temperature sufficiently high to eliminate Water and below the pyrolytic point of the reactants and resultants of reaction; with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a glyoxalderived substituted methylene bridge connecting the amino nitrogen atom with a resin molecule; with the further proviso that the ratio of reactants be approximately 1, 2 and 1 respectively; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible.

6. The process of breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including synthetic hydrophile products obtained by condensing (a) an oxyalkyladon-susceptible, fusible, non-oxygenated organic solventsoluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin mole cule; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of phenols of functionality greater than 2; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom and reactive toward glyoxal; and1(c) glyoxal said condensation reaction being conducted at a temperature sufficient-ly high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; with the proviso that the condensation reaction be conducted so as to produce a significantportion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a glyoxalderived substituted methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the ratio of reactants be approximately 1, 2 and 1, respectively, with the further proviso that said procedure'involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylationsusceptible.

7. The process of breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including synthetic hydrophile products obtained by condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated organic solventsoluble, water-insoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of phenols of functionality greater than 2; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom and reactive towards glyoxal; and (c) glyoxal, said condensation reaction being conducted at a temperature sufficiently high to eliminate Water and below the pyrolytic point of the reactants and resultants of reaction; with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a glyoxal-derived substituted methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the ratio of reactants be approximately 1, 2 and 1, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible.

8. The process of breaking petroleum emulsions of the water-in-oil type characterized by'subjecting the emulsion to the action of a demulsifier including synthetic hydrophile products obtained by condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated organic solvent- "soluble, water-insoluble, low-stage phenol-formaldehyde in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom and reactive towards glyoxal; and (c) glyoxal, said condensation reaction being conducted at a temperature sufliciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a glyoxal-derived substituted methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the ratio of reactants be approximately 1, 2 and 1, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation susceptible.

9. The process of breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including synthetic hydrophile products obtained by condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated organic solventsoluble, water-insoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 5 phenolic nuclei per resin molecule; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of phenols of functionality greater than 2; said phenol being of the formula proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a glyoxal-derived substituted methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the ratio of reactants be approximately 1, 2 and 1, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible.

10. The process of breaking petroleum emulsions of in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom and reactive towards glyoxal; and (c) glyoxal said condensation reaction being conducted at a temperature above the boiling point of water and below C., with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a glyoxal-derived substituted methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the ratio of reactants be approximately 1, 2 and 1, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible.

References Cited in the file of this patent UNITED STATES PATENTS 2,414,729 Fleming et a1 Jan. 21, 1947 2,425,175 Carpenter Aug. 5, 1947 2,454,544 Bock et a1. Nov. 23, 1948 2,457,634 Bond et al Dec. 28, 1948 2,507,910 Keiser et a1. May 16, 1950 2,679,485 De Groote May 25, 1954 

1. THE PROCESS OF BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER INCLUDING SYNTHETIC HYDROPHILE PRODUCTS OBTAINED BY CONDENSING (A) AN OXYALKYLATION-SUSCETIBLE, FUSIBLE, NON-OXYGENATED ORGANIC SOLVENT-SOLUBLE, WATER-INSOLUBLE, LOW-STAGE PHENOLALDEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF PHENOLS OF FUNCTIONALITY GREATER THAN 2; SAID PHENOL BEING OF THE FORMULA 